Process of producing high quality carbon black



1941- H. VOLLBRECH T ETAL 2,228,543

' rnocsss OF PRODUCING HIGH QUALITY CARBON BLACK 1 Filed May :5, 1937 i .F' r f 05 j a t I V &

lnverziow T f1krwmzflrvyblhbrechf" hard fiupe Patented Jami/1,1941 v 2,228,543

UNITED STATES PATENT QFFICE A ,azam A I raocnss or moimomo HIGH QUALITY CARBON BLACK Hermann Voilbrecht and Richard 'Hupe, Frankfort-on-the-Main, Germany, assignors, by

mesne assignments, to.Cl1eniical Marketin Company Inc.,' New York, N. Y.

Application May 3, 1937, Serial No. 140,442

In Germany May 8, 1936 I 7 Claims. (01. 23-209.

The present invention relates to the art of in such manner that about 100 explosions per manufacturing carbon black and, more particu-y. minute are produced. The composition of the larly; to an improved process of producing high gas to be treated is as follows:

quality carbon black from hydrocarbons. v v

Heretofore, various processes have been used Constituent 1, 4mm 5 for the production of carbon black. It was al ready known that acetylene, ethylene or their v p m mixtures with each other, with methane or with g 2 other hydrocarbons may be utilized for produc- 1 010 ing carbon black on a commercial scale.' Rel0 cently. a very successful'and efiicient process has "70:0 been introduced for the production of carbon black involving the explosion of hydrocarbon gas mixtures containing predetermined amounts of 7 ,f gfgg g fi gggffi oxygen. the expios1ve decomposition being carg. ried out at normal or at elevated pres-sures. It The l wer lgmtwn hmlt at a ut 6 mosph res ha b e found th t a high t rb bla k initial pressure is at an oxygen concentration of can be produced by exploding mixturesof such about 28%. Only carbon b c W p c y hydrocarbons with a quantity of oxygen consid useless qualities may be obtained in this manner. erably greater than the minimum required for The experimental results for different Oz concen- 2O the formation of an explodible mixture at eletration of the-mixture are the following:

vated pressures. In order to increase the ou p t of the apparatus, the explosions were produced Carbon black- Rubbe'rmfing' in rapid succession so that the carbon black pro- 1 yield i duced was removed from the reaction chamber by Q? in the initial g gglgr a Breaking r the rapid expansion of the residual gases; Gengas Percent t n factor elqnga' a erally, a surge or storage tank was interposed gg z kgJcmrla between the mixing device and the reaction I chamber. By means of this surge tank, the .8 1.50 103 403 pressure was maintained practically constant 2523 and, what is of great importance, alsothe constitution of the mixture was maintained substaniially constant. From the surge or storage tank, When m ning the coloring S gth coeflithe mixture was passed to the reaction or exploe a r the p h f 0 0f t e bon s sion chamber by it bl l t and conduit compared with the commercial Sechsbrand car- 5 means. In the: reaction chamber, the explodibie n s a standard and h me (heavy spar) i mixture was ignited by conventional ignition ture and'taking the coloring depth of the Sechsmeans h as a spark plug incandescent wire, or brand carbon as the unit. The test with rubber in m cases merely by thehigh compression of is carried out in the conventional manner. The

0 the mixture. A process of this character is disnumbers E Q D t0 ge fi u s Ob- 40 closed in the co-pending application of Lajos von tained from a number of tests with different Szeszich, Serial No. 33,824, filed July 30, 1935, ration of the vulcanization- The spo d whi h issued as s p t 2 150 79 n values for the well known American rubber car- March 14, 1939. I bon are: I I v In accordance with this recent patent,a gas kin t h 2 45 obtained by decomposition of a cokeoven gas is a g 53255 1111:3 5

treated in connection with oxygen and at an e initial pressure of about 6 atmospheres. The ig- In the waste gases which according to the reacnition of the gas mixture is carried out by means tion conditions contain about 24-35% CO, about of a glow wire and the operation is regulated 51 to 57% H2, about 15 to 2% CH4, and about to 85% of the heating value of the gases used is retained.

The introduction of the gases is preferably effected by means of two compressors, of which the one (a) (Fig. 1) propels and/or compresses the gases containing carbon while the other (b) propels and/or compresses the oxygen or the gas mixture containing oxygen. The mixing of the two reaction constituents is preferably carried out in a mixing arrangement or chamber (0) before entering the reaction vessel. The adjustment of the desired mixture proportion of the two gases is obtained by adjusting the output of the two compressors or by means of conventional automatic mixing controls. It is advisable to provide a pressure resistant tank (1') between the mixer and the reaction vessel (at), this tank should have a capacity which is multiple of that of the reaction vessel. This tank makes it possible to uniformly fill up the reaction chamber to the desired working pressure, and, on the other hand, it prevents the sudden occurrence of gas mixtures which are either too rich in oxy en or too poor in oxygen so that they are not capable of exploding. Such variations would otherwise occur due to the irregularities in the operation of the compressors. In the reaction vessel (d) the mixture of carbon-containing substances and oxygen-bearing gases is exploded to form carbon black and a combustible gas. The reaction products leaving the reaction vessel in the manner of a stroke and comprising gas and carbon black are conducted to a suitably dimensioned carbon separator (e). The separation of carbon is preferably carried out in such manner that the reaction products are tangentially introduced into a drum-like container. By means of this separator, the greater part of the carbon produced is separated from the waste gases which contain but little carbon and are led into a filter (f) for complete purification or into an electrical dust collecting system. Preferably, both the carbon separator and the cleaning system are maintained at a temperature which is above the dew point of the combustion or waste gases, so that the water produced by the reaction does not precipitate together with the carbon. This makes subsequent drying of the carbon unnecessary and prevents clogging of the filter. The waste gas after being completely freed from carbon is introduced into a cooler (g) in order to deposit the water formed during the reaction which is separated in separator (h) from the waste gas.

Although this process has been very satisfactory and permitted to produce carbon black of excellent quality on a practical and industrial scale, various difiiculties have been experienced in the practical operation. Thus, it has been found that already a short time after the operation of the apparatus has been started, self-in nition of the explosive mixture was caused, even though the apparatus was carefully cooled. In other words, the explodible gas mixture was automatically ignited and exploded as soon as it was introduced into the reaction chamber and without the actuation of the ignition means therein. In most cases the ignition means have been only used when the reactiton or the operation of the apparatus was started and have been completely disconnected hereafter. This form of operation was satisfactory to a certain extent, however, frequently the explosion of the gas mixture through the self-ignition occurred so soon after the introduction of the gases or ,even during the introduction thereof that the explosion would backfire into the surge tank or even further back into the conduits causing dangerous and destructive explosions or at least serious interruptions in the smooth operation of the plant. Of course, the danger of these explosions considerably increased the operating costs and thus has reduced the efficiency of the carbon producing plant.

We have discovered that the dangers and disadvantages inherent to the self-ignition of explodible hydrocarbon mixtures may be eliminated in a simple and efficient manner.

It is an object of the present invention to provide an improved process for producing highquality carbon black from explodible mixtures of hydrocarbons and of oxygen-containing gases which completely eliminates the disadvantages and dangers connected with the automatic or self-ignition of the explodible mixtures.

It is another object of the present invention to provide a novel and improved process of producing high-quality carbon black from explodible mixtures of hydrocarbons and oxygen-containing gases by a rapid succession of explosions without dangerous and undesirable permature explosions or backfiring.

It is a further object of the present invention to provide a process of producing high-quality carbon black by introducing an explodible mixture of hydrocarbon gases, and of oxygen-containing gases into a reaction chamber involving critical control of the rate, period and velocity of the introduction of the gas mixture.

The invention also contemplates an improved process for the production of high qualtity carbon black from explodible gas mixtures by means of rapidly following explosions which may be readily carried into practice on a practical and industrial scale and without requiring any complicated'or costly changes in existing installations.

Other and further objects and advantages of the invention will become apparent from the following description.

Broadly stated, according to the principles of our invention the disadvantages and dangers of automatic or self ignition or backfiring can be avoided in a simple and positive manner by providing critical control of the time during which the initial materials are introduced into the reaction chamber. We have discovered that the back firing is successfully avoided by providing inlet periods of the reaction gases which are shorter than 0.5 second and are preferably of the order of 0.01 second. Surprisingly, under these conditions the danger of backfiring is completely avoided even in the case when a surge tank or the like is connected before the reaction or explosion chamber. It has been also ascertained that further advantages are obtained by providing a constant velocity of the explodible gases when they are introduced into the reaction chamber during the limited inlet periods accord ing to the principles of the invention. These critical operating conditions can be accomplished in an advantageous manner by maintaining the pressure in the surge tank at a pressure considerably higher, but at least 1 times as high than the desired inlet pressure prevailing in the reaction chamber.

The desirable constant rate and velocity of admission during the inlet period is accomplished according to the invention by providing such control and actuation of the inlet means or valves that reduction in the inlet pressure during the to completely oxidize all the, carbon present, es-- inlet period is compensated for by increasing the cross section through which the gases are introduced into the reaction chamber. In this manner substantially constant inlet velocities of the gas mixture are maintained. At the end of the inlet period it is preferred to provide a sudden, stroke-like closure of theinlet means. Although the cause of self ignition is not completely determined, it appears that the catalytic effect of the carbon formed and remaining in part in the reaction chamber may be at leastin part responsible therefore. Ofcourse, the principles and the advantages of our invention are clear irrespective of the circumstance whether this explanation is correct or only approximative.

In order that those skilled in the art may have a better understanding of the invention, the following detailed description is given.

Hydrocarbon gases are compressed'by a compressor or some other conventional means. Oxygen-containing gases are likewise compressed-by a second compressor or other corresponding means. The compressed gases are introduced into a mixing device in such a proportion that considerably more oxygenis present in the mixture than the minimum necessary for producing an explodible mixture but at the same time the oxygen is insufficient for oxidizing all of the carbon present. The explodible mixture thus provided is now introduced into a surgeor storage tank. The pressure of the mixture in thesurge tank is maintained at a value which is considerably higher, preferably at least 1.5 times higher than the preferred initial pressure in the reaction chamber. Valve or nozzle means are provided for admitting the explodible mixture into the reaction chamber. The inlet means are so constructed and arranged that the inlet cross section is substantially in inverse proportion with the pressure differential between the, inlet main and the reaction chamber; Thus, when the difference in pressure between the inlet main and the reaction chamber becomes less, the cross section through which the gasesare'admitted into the reaction chamber is increased. .This will maintain substantially constant inlet velocities and will insure inlet periods which are less than about 0.5 second and are preferably of the order of 0.01 second. Preferably, thevalve is automatically actuated by the dropin pressure on the inlet main. It is of importance to insure that the valve is closed tightly at the end of each inlet period in a stroke-like manner and that it remains in such closed position during the full reactionperiod. x

Although the present invention has been described in connection with, a preferred embodiment thereof, variations and modifications may be resorted to by those skilledin the art without departing from the principles of the present invention. I We consider all of .these variationsand modifications as within the true spirit and scope of the present invention-as disclosed in-the present description and defined by the appended claims.

We claim: x

1. The process of producing high quality carbon black which comprises compressing gases containing hydrocarbons, compressing gases containing oxygen, mixing said compressed gases to form a compressed mixture containing hydrocarbon gases and oxygen-containing gases wherein the oxygen content is about 40% and considerably greater than that necessary to form an ex plodible mixture but less than that necessary tablishing abody of said explodible gas mixture having a volume several times that of a reaction chamber and having a substantially constant constitution and pressure,ma'intaining a pressure on said bodyof gas mixture greater'than the initial filling pressure of a reaction chamber,

passing a portion of said body of gas mixture in the form of a stream of gas to said reaction said carbon'black by a practically adiabatic expansion of saidresidual gases whereby. premature explosions of said explodible'gas mixture'are avoided. a I 1 2. The process of producing highquality c bon black which comprises compressing gases containing hydrocarbons, compressing oxygen containing gases, mixing said compressed. gases to form a compressed mixture containing hydrocarbon'gases and oxygen-containing gases where- .in the oxygen content is considerably greater than that necessary to form an explodible mixture but lessgthan that necessary to'completely oxidize all the carbon present, pumping said compressed gas mixture to a surgev tankto establish a substantial body of gas mixture there in and to maintain the i constitution and pressure of said body substantially constant, maintaining a pressure on said body of gas mixture about 1.5 times as great as the initial filling pressure of a reaction chamber, passing a portion-of. said gas mixture from said surge tank as a st'ream'of. gas to 'said reaction chamber, varying the cross section of jsaid gas streamin accordance with the change in the difference in pressure betweensaid gas stream and said reaction chamber, filling said reaction chamber with said gas stream during a period of about 0.01 second, closing; saidrea ction chamber, exploding'the contents of said'reaction chamber to form carbon blaclr'and residual gases containing hydrogen and carbon monoxide and removing said carbon black bya prac tically adiabatic expansion of said residual gases whereby premature explosions of said explo'dible gas mixture are avoided. f

3. The process of producing high quality carbon black from hydrocarbon gases which comprises forming a mixture containing hydrocarbon gases and oxygen-containinggases. at elevated pressures wherein the oxygen content is considerably greater than that necessary to form an explodible mixture but less than that necessary to completely oxidize all the carbon pres-, ent, establishing a body of said explodible mixture having a volumeseveral times thatof a reaction chamber to maintain the constitution and the pressure thereof substantially constant, maintaining said. .body at a pressure considerably greater than the initial filling pressure of a reaction chamber, conveying portions of said body of gas mixture as streams of gas to said reaction chamber, varying the cross section of said gas streams inverselyin proportion to the change I in the difference of pressure between said gas streams and the pressure of said reaction chamber to fill said reaction chamber with said gas streams during peroids of not more than about 0.5 second and at a rate sumciently rapid to substantially eliminate propagation of the subsequent explosion to that portion of the explodable mixture yet to be introduced into the reaction chamber, closing said reaction chamber after each filiing, exploding the contents of said reaction chamber after each filling to form carbon black and residual gases containing hydrogen and carbon monoxide, opening said reaction chamber after each explosion and expelling said carbon black whereby said reaction chamber is filled at a practically constant rate and premature explosions of said explodable gas mixtures are avoided.

4. The process of producing high quality carbon black which comprises forming an explodible mixture containing hydrocarbon gases and oxygen-containing gases under elevated pressure wherein the oxygen content of about 40% 0! said explodible mixture .is considerably greater than that necessary to form an explodible mixture but less than that necessary for, complete oxidation of all the carbon present, establishing a body of said explodible mixture having a volume greater than that of a reaction chamber to maintain the constitution and the pressure thereof substantially constant, maintaining said body at a pressure greater than the initial filling pressure of a reaction chamber, passing a portion or said body of gas mixture to said reaction chamber as a'stream of gas while restricting the cross section of said gas stream inversely in proportion to the pressure differential between said body of explodible gas mixture and said reaction chamber to fill said reaction chamber at a substantially constant rate during a period of not more than 0.5 second, said period being short enough to limit propagation of the subsequent explosion to that portion of said explodible gas mixture yet to be introduced into said reaction chamber, closing said reaction chamber, igniting the contents of said reaction chamber to obtain an explosion and to form carbon black and residual gases, and opening said chamber and expelling said carbon black whereby premature explosions of said explodible mixture are avoided.

5. The process of producing high quality carbonblack which comprises establishing a body of an explodible mixture as a stream of gas containing hydrocarbon gases and oxygen-containing gases wherein the oxygen content of about 40% is considerably greater than that necessary to form an explodible mixture but less than that necessary for complete oxidation of all the carbon present, said body of explodible mixture having a volume several times greater than that of the reaction chamber and having a substantially constant constitution and pressure, maintaining said body at a pressure greater than the initial filling pressure of a reaction chamber, introducing a portion of said body of explodible mixture as a stream of gas at elevated pressures into said reaction chamber while restricting the cross-section of said gas stream inversely in proportion to the pressure difierential between said body of explodible mixture and igniting the contents of said reaction chamber to produce an explosion and form carbon black and residual gases, opening said reaction chamber, expelling said carbon black by a practically adiabatic expansion of said residual gases and repeating the aforesaid steps in rapid succession whereby premature explosions of said explodible mixture are avoided.

6. The process of producing high quality carbon black which comprises establishing a body of explodible mixture containing hydrocarbon gases and oxygen wherein said oxygen content is about 40% and greater than that necessary to form an explodible mixture but less than that necessary for complete oxidation of all the carbon present, said body of explodible mixture having a substantially constant constitution and pressure, and having a volume several times that of a reaction chamber, maintaining said body at a-pressure greater than the initial filling pressure of a reaction chamber, intermittently introducing portions of said body of explodible mixture at elevated pressures into said reaction chamber as streams of varying cross section, the cross sections of said streams being varied-inversely in proportion to the pressure differential between said body of explodible mixture and said reaction chamber at a substantially constant rate during periods of about 0.01 second, exploding the contents of said reaction chamber after introducing each of said portions to form carbon black and residual gases containing hydrogen and carbon monoxide, and expelling said carbon black, whereby said reaction chamber is filled at a substantially constant rate and premature explosions are avoided.

7. The process of producing high quality car bon black which comprises establishing a body of an explodible mixture having a volume greater than that of a reaction chamber and containing hydrocarbon gases and oxygen wherein said. oxygen content of about 40% is considerably greater than that necessary to form an explodible mix ture but less than that necessary for complete oxidation of all the carbon present, said body of explodible mixture having a substantially constant temperature and pressure, maintaining said body at a pressure greater than the initial failing pressure of'a reaction chamber, introducing a portion of said body of explodible mixture as a stream of gas at elevated pressures into said reaction chamber while restricting the cross sec- 4 tion of said gas stream inversely in proportion to the pressure diiferential between said body of explodible mixture and said reaction chamber to fill said reaction chamber at a substantially constant rate during a period of not more than'about 0.5 second and exploding the contents of said reaction chamber whilst said chamber is closed to form carbon black whereby premature explosions are avoided.

HERMANN VOLLBRECHT.

RICHARD HUPE. 

